Blocked oligomeric isocyanates, their production and use

ABSTRACT

Self-dispersible mixtures (G) of oligomeric isocyanates (C) reacted in part with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B) are useful as auxiliaries in the finishing of fibrous material with oleophobicizing and/or hydrophobicizing finishes (F) comprising fluorocarbon polymers.

BACKGROUND OF THE INVENTION

A popular way of conferring an oil-repellent and/or water-repellentfinish on textile material is to use fluorocarbon polymers which providea certain air and vapour permeability and also an easy care finish, toproduce, for example, breathable finishes which are impermeable towater. For general use it is desirable for the finish to have certainfastnesses, particularly cleaning fastnesses, among which the fastnessto washing, especially the permanence to washing, plays a particularrole; a problem in this is that an impairment of the oleophobic and/orhydrophobic effect of the finish due to a clean with customary householddetergents (by washing or shampooing, for example) requires a thermalafter treatment, for example at 140° C. or higher (by ironing, forexample), to be at least partially recovered—provided there is stillproduct on the substrate after the clean. It is therefore especiallydesirable for the original properties (particularly the oil- andwater-repellent properties and the vapour permeability or the easy careproperties) to be essentially intact after one or more cleaning orwashing operations, even without a thermal aftertreatment, if possible.

DE 19615116 A1 describes blocked polyisocyanates as crosslinker resinsfor organic polyhydroxy compounds for clearcoating baking finishes,these blocked polyisocyanates being prepared by reacting anisocyanurate-group-containing (cyclo)aliphatic polyisocyanate with anonionic hydrophilic component (a Carbowax, for example), amonofunctional blocking agent and a hydrazide-group- containingstabilizing component and optionally certain chain extenders in acertain quantitative ratio, by first reacting the startingpolyisocyanate in a non-exhaustive manner with the hydrophilic componentand then with the blocking agent and thereafter reacting with thestabilizer and optionally with the chain extender.

EP 0537578 A2 describes the use, together with fluorochemicals, ofblocked polyisocyanates which contain polyalkylene ether and havebuilt-in ionic groups for the hydrophobicizing and oleophobicizingfinishing of textiles. Such ionically modified products have thedisadvantage that they are not necessarily compatible with otherproducts of opposite ionicity, for example anionically modified productsand synthetic resin components having a cationic character, since thiscan lead to precipitates in an aqueous medium.

Later U.S. Pat. No. 5,714,082 describes water- and oil-repellent,soil-repellent finishes with fluoro-chemicals, the use of an extender ofthe hydrocarbon urethane type (there the nonionic product HCT-3) inExample 42 thereof being designated as contributing to “deficiencies”.

It has now been found that using the hereinbelow defined mixtures (G) ofblocked oligomeric isocyanates surprisingly makes it possible to improvethe oil- and water-repellent properties and also the fastnesses of thefinishes mentioned at the outset.

SUMMARY OF THE INVENTION

The invention relates to the defined mixtures (G), compositionscomprising these mixtures, the production of the mixtures and their use.

In a first aspect, the invention accordingly provides self-dispersiblemixtures (G) of oligomeric isocyanates (C) reacted in part withpolyethylene glycol monoalkyl ether (A), which optionally containspropyleneoxy units, and optionally with a chain extender (K) andexhaustively blocked with an isocyanate-blocking pyrazole (B).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The self-dispersible mixtures (G) can be formulated with water andoptionally further additives to form aqueous dispersions (D).

The process for the production of the self-dispersible mixtures (G) isespecially characterized in that

in a first process step

(a) a minor proportion of the isocyanate groups in the oligomericisocyanate (C) are reacted in the absence of protogenic solvents withpolyethylene glycol monoalkyl ether (A), which optionally containspropyleneoxy units, to form a product (U1) and this product (U1) is thenoptionally converted into a product (U2) which has a higher NCO-basedequivalent weight and which still contains reactive NCO groups,

and in a second process step

(b) the remaining isocyanate groups are exhaustively blocked withisocyanate-blocking pyrazole (B).

For the production of the aqueous dispersions (D), the mixtures (G) thusproduced can, preferably directly after their production, be mixed withwater and optionally further additives.

As oligomeric isocyanates (C) are suitable generally known isocyanates,advantageously having two to ten NCO groups, for example hydrocarbonoligoisocyanates or oligomers of hydrocarbon diisocyanates, especially

(C₁) oligomers of aliphatic diisocyanates or

(C₂) diphenylmethane diisocyanate or polyphenylenepolymethylenepolyisocyanates.

The monomeric aliphatic diisocyanates from which the oligomers (C₁)derive preferably have at least one isocyanate group bonded to amethylene. The oligomeric isocyanates (C₁) can be for example di-, tri-or tetramers of aliphatic, optionally cyclic diisocyanates having forexample 2 to 16, preferably 4 to 10, carbon atoms in the basichydrocarbon skeleton. Of these, hexamethylene diisocyanate, isophoronediisocyanate and 2,4,4-trimethylhexylene-1,6-diisocyanate are preferred,especially hexamethylene diisocyanate. The oligomers can be cyclic oropen-chain; suitable trimers include in particular those having anisocyanurate or biuret structure, while suitable dimers includeespecially those having a uretidione structure; optionally it is alsopossible to use oligomers thereof.

The ether-forming alkyl radicals in (A) are in principle discretionary,but are preferably of low molecular weight; they preferably contain 1 to4 carbon atoms. If desired, (A) can also contain propyleneoxy groups, inwhich case, however, the ethyleneoxy groups preferably outweigh thepropyleneoxy groups.

The polyethylene glycol monoalkyl ethers (A), which optionally containpropyleneoxy units, preferably conform to the average formula

R—(O—CH₂—CH₂)_(n)—OH  (I),

where

R is C₁₋₄-alkyl-(O-propylene)_(m)-,

n is from 5 to 30 and

m is from 0 to 10,

subject to the proviso that m is ≦⅓ of n.

is preferably from 8 to 24, particularly preferably from 12 to 20.

m is advantageously ≦¼ of n and is for example from 0 to 4, preferablyzero.

In the first process tep (a), the oligomers (C) are first reacted witholigoethylene glycol monoalkyl ether (A), which optionally containspropyleneoxy units, the quantitative ratio of (A) to (C) being selectedin such a way that only a portion of the available isocyanate groups isreacted with (A). The mixing ratio of (A) to (C) is advantageouslyselected in such a way that more than one mole equivalent of (C) is usedper mole of (A). One equivalent of (C) is the weight, determinable bytitration, which corresponds to one NCO group. One mole equivalent of(C) is this number in grams. The equivalents ratio of (A) to (C) isconsequently the ratio of the number of moles of (A) to the number ofmole equivalents of (C). This ratio is chiefly within the range from1/50 to 1/2, preferably within the range of 1/40 to 1/4, particularlypreferably within the range from 1/30 to 1/10.

The reaction of (A) with (C) can be carried out in the presence orabsence of solvents, in which case suitable solvents are advantageouslynon-protogenic solvents, for example propylene carbonate, acetone,methyl ethyl ketone or methyl isobutyl ketone. When no (K) is used, thereaction is preferably carried out in the absence of solvents. Thereaction takes place for example at elevated temperature,advantageously >30° C., for example at temperatures within the rangefrom 60 to 95° C., and advantageously under an inert atmosphere, forexample under argon or preferably nitrogen.

The reaction of (A) with (C) first gives rise to an alkyl polyglycolether urethane product (U1), which contains urethane groups resultingfrom the reaction of the hydroxyl group in (A) with a portion of theisocyanate groups in (C) and preferably conforming to the formula

R—(O—CH₂—CH₂)_(n)—O—CO—NH—  (u).

Depending on the molar ratio of (A) to (C), the content of urethanecomponents in (U1) can vary, so that the reaction product (U1), besidesurethane components, can also contain unreacted components which arefree of urethane groups derived from (A), i.e. fractions of (C) whichhave essentially not reacted with (A).

Prior to the further reaction with (B), the isocyanate-group-containingproducts (U1) can optionally be converted intoisocyanate-group-containing products (U2) having a higher NCO-basedequivalent weight.

The conversion into (U2) can advantageously be effected by inter- and/orintramolecular further reaction of (U1) or also by addition of suitable,preferably low molecular weight, chain extenders (K).

The inter- or intramolecular further reaction of (U1) can be effected byheating, for example at temperatures within the range from 60 to 95° C.,since, as the reaction time to prepare (U1) at elevated temperature isextended, the NCO-based equivalent weight will gradually rise beyondthat which stoichiometrically corresponds to simple urethane formation(U1). As a result, for example, further NCO groups may be made to becomeinvolved, for example through formation of allophanate, uretidioneand/or isocyanurate structures. The progress of the reaction can bemonitored by determining the equivalent weight based on isocyanategroups.

Suitable chain extenders (K) for the reaction of (U1) with a chainextender (K) are generally difunctional compounds, i.e. compounds whichcontain at least two (e.g. 2 to 5) reactive hydrogen atoms capable ofreaction with isocyanate groups, chiefly hydroxyl groups and/or primaryamino groups, and which in particular do not introduce any ionic groups.Suitable (K) for the purposes of the invention include chiefly aliphaticdiols, diamines or aminoalcohols which contain 2 to 6 carbon atoms andin which, if they contain 4 to 6 carbon atoms, the aliphatic radicalscan optionally be interrupted by oxygen, or also especially water, waterbeing included among the chain extenders (K) insofar as it will takepart in a two-step reaction (with CO₂ elimination) according to thegeneral reaction scheme

R₀—NCO+H₂O→R₀—NH₂+CO₂

R₀—NH₂+OCN—R₀→R₀—NH—CO—NH—R₀

which leads to urea bridging. Specific examples of (K) are ethyleneglycol, propylene glycol, butylene glycol, 1,4-butanediol, hexyleneglycol, diethylene glycol, triethylene glycol, dipropylene glycol,ethylenediamine, tri-, tetra-, penta- or hexamethylenediamine,ethanolamine, isopropanolamine and water, of which the diols, especiallyethylene glycol and propylene glycol, and particularly water arepreferred.

The reaction with (K) can advantageously take place in the presence ofsolvents, preferably within the temperature range from 20 to 95° C.,temperatures within the range from 20 to 60° C. being already suitableif the reaction is carried out in the presence of a catalyst of the typeknown for the preparation of polyurethanes, for example dibutyltindilaurate, diacetate or dioctoate.

It is surprisingly particularly advantageous for the invention to use areaction product (U2) in which the isocyanate-based equivalent weighthas risen beyond that which stoichiometrically corresponds to simpleurethane formation in reaction product (U1). The isocyanate-basedequivalent weight of (U2) is advantageously by 1 to 20%, preferably 2 to15%, more preferably 3 to 12%, higher than that which stoichiometricallycorresponds to single urethane formation in (U1). The desired or optimumdegree of conversion for a certain combination of starting materials (A)and (C) and optionally (K) can be determined by means of a fewpreliminary experiments. When a chain extender (K) is used for preparing(U2), then the ratio of the number of moles of (K) to the number of moleequivalents of (U1) is advantageously in the corresponding suitablerange for achieving the aforementioned increase in the NCO-basedequivalent weight, especially within the range from 0.01 to 0.16 mol of(K), advantageously 0.02 to 0.12 mol of (K), preferably 0.03 to 0.1 molof (K), per mole equivalent of (U1).

The reaction products (U1) and (U2) are generally mixtures. The products(U1) can thus be for instance random mixtures of differingly convertedproducts or, when, for example, the equivalents ratio of (C)/(A) isgreater than the degree of oligomerization in (C), (U1) is particularlya mixture of products which contain a radical derived from (A) andproducts which do not contain a radical derived from (A). Correspondingfurther mixtures are formed in (U2).

The reaction products (U1) or preferably (U2) can then be reacted with(B).

The isocyanate-blocking pyrazoles (B) used can generally be anypyrazoles known to be useful for blocking or masking polyisocyanates,for example as described in EP-A 0500495, particularly those wherein thesubstituents optionally present on the pyrazole ring are non-ionogenicand also non-NCO-reactive (i.e. they do not react with NCO groups andtherefore do not interfere with the blocking reaction either). Aspyrazoles (B) can advantageously be employed those of the averageformula

where

R₁, and R₂ R₃ are each, independently of the others, hydrogen, alkyl,allyl, aralkyl, aryl or alkoxy or

R₂ and R₃ together with the carbon atoms to which they are bonded, forma benzenic ring which is condensed to the pyrazole ring and isoptionally substituted with alkyl, aryl or alkoxy.

In the formula (II), the alkyl and alkoxy groups advantageously contain1 to 3 carbon atoms, aryl is preferably phenyl, aralkyl is preferablybenzyl; when R₂ and R₃ together with the carbon atoms to which they arebonded form a condensed benzenic ring, this benzo ring is preferablyunsubstituted. R₂ is advantageously hydrogen, C₁₋₃-alkyl, benzyl orallyl. R₁ and R₃ are each, independently of the other, advantageouslyhydrogen or C₁₋₃-alkyl. C₁₋₃-Alkyl is preferably methyl. R₂ isparticularly preferably hydrogen.

Particularly preferred pyrazoles (B) are those of the formula (II)wherein R₁ is hydrogen or methyl, R₂ is hydrogen and R₃ is methyl.

The reaction of the pyrazoles (B) with (U1) or preferably with (U2) canbe effected by simply bringing the reagents together, for example byaddition of (B) into the reaction product (U1) or preferably (U2),advantageously directly after its synthesis. The blocking of theisocyanate groups with the pyrazole (B) can take place in the presenceor absence of a catalyst (e.g. dibutyltin dilaurate, dioctoate ordiacetate), preferably in the absence of catalysts. The reaction isexothermic, and initial gentle heating is sufficient to get the reactiongoing. The reaction is advantageously carried out within the temperaturerange from 15 to 60° C. The amount used of pyrazole (B) is expedientlysufficient to exhaustively block the isocyanate groups which are presentin the employed product (U1) or (U2)—which may be determined bytitration, for example. The reaction with (B) is advantageously alsocarried out under an inert atmosphere, for example under argon orpreferably nitrogen, as described above for the synthesis of (U1).

The product thus prepared is a mixture (G)—at least to the extent that(U1) or (U2) is a mixture—and is essentially nonionic andself-dispersible in water, i.e. it forms very fine, aqueous dispersionsby simple addition of water or by simply stirring it into water, evenwithout the assistance of emulsifiers or other surfactants. The aqueousdispersions (D) of the mixtures (G) also form part of the subject-matterof the present invention. They are preparable in a conventional manner,by simply stirring (G) into water, or vice versa; if desired, it is alsopossible to add further additives, for example a non-ionogenic,surface-active stabilizer (E) and/or a solubilizer (L).

Suitable non-ionogenic stabilizers (E) are chiefly addition products ofethylene oxide to polypropylene glycol or to an aliphatic and/oraromatic alcohol having, for example, 9 to 24, preferably 11 to 18,carbon atoms, the degree of oxyethylation being advantageously such thatthe HLB is advantageously ≧8, preferably within the range from 10 to 18.Block polymers of ethylene oxide and propylene oxide which have theappropriate HLB are also suitable. When a non-ionogenic stabilizer (E)is used, it is advantageously used in smaller amounts than (G), forexample within the range from 0.5 to 40%, preferably 1 to 20%, based on(G).

The concentration of (G) in the aqueous dispersions (D) is of itselfdiscretionary; for concentrated dispersions (D) it is advantageouslywithin the range from 5 to 70% by weight, preferably 10 to 60% byweight, based on total dispersion (D).

Examples of suitable solubilizers (L) are mono- or oligoalkylene glycolsand their C₁₋₄-alkyl monoethers (e.g. ethylene glycol, propylene glycol,hexylene glycol, dipropylene glycol, dipropylene glycol monomethylether, mono- or diethylene glycol monobutyl ether), ethylene carbonate,propylene carbonate or N-methylpyrrolidone.

When solubilizers (L) are used, their concentration in (D) may varywithin wide limits, for example within the range from 1 to 30% byweight, based on the total weight of (D), but is advantageously inferiorto the concentration of (G), for example within the range from 5 to 80%by weight of (G).

If desired, the dispersions (D) may include an additive (Z) forprotection against microbial damage, especially a microbicide and/or anadditive which inhibits fungal and/or bacterial growth. Suitable forthis purpose are generally commercially available products, which can beused in the small amounts (e.g. <2% by weight) which are recommended ineach case.

The aqueous dispersions (D) of the invention are, in particular, of veryfine particle size. The particle size of the dispersed particles is forexample within the range from 0.01 to 1 μm, preferably 0.05 to 0.5 μm.The dispersions (D) are also very stable in storage—particularly thosecomprising (E) and/or (L)—and readily pourable. They retain theirapplication and physical properties even after prolonged storage.

The mixtures (G) of the invention, advantageously in the form of theiraqueous dispersions (D), serve as auxiliaries in the oil- and/orwater-repellent finishing of fibre material with fluorocarbon polymers(F).

Suitable fluorocarbon polymers (F) are generally any of those polymerswhich contain perfluoro-hydrocarbon radicals (“fluorocarbon radicals”)and which are known to be used for oil- and/or water-repellent finishes.The fluorocarbon radicals are chiefly perfluoroalkyl radicals,especially monovalent radicals R_(F) of the formula

—C_(p)F_((2p+1))  (f),

where p is from 3 to 21, preferably 4 to 16, or also those wherein afluorine atom has been replaced by a chlorine atom.

These radicals R_(F) can be linear or also branched; preferably they arelinear. They are preferably radicals of the formulae

or

where

q is from 3 to 15, preferably 5 to 13, and

r is from 2 to 12, preferably 2 to 8.

They can for example be attached to a polymer main chain directly or viaa low molecular weight aliphatic radical and optionally via an ester orether bridge; optionally, they may also be attached to the low molecularweight aliphatic radical via an amide group. The polymer main chain isgenerally a hydrocarbon chain as produced by free-radical polymerizationof ethylenically unsaturated monomers, for example from appropriatevinylic or (meth)acrylic monomers.

The radicals R_(F) can for example also be attached, via a bridgingmember, to a nitrogen compound, for example to a condensation product ofan aldehyde and a urea or melamine, chiefly to etherified methylolderivatives of urea or heterocyclic nitrogen compounds, particularly ofan optionally cyclic urea (e.g. N,N′-dimethylolurea,N,N′-dimethylolethyleneurea, N,N′-dimethylolpropyleneurea orN,N′-dimethyloldihydroxyethyleneurea or a precondensate thereof) or of amethylolmelamine (e.g. tri-to hexamethylolmelamine), as condensateswhich are heat-curable optionally in the presence of suitable catalysts.

The fluorocarbon polymers (F) are chiefly

(F_(A)) copolymers which contain constituent comonomer units containingfluorocarbon radicals R_(F) or

(F_(B)) nitrogen-containing polycondensates which contain fluorocarbonradicals R_(F).

Copolymers (F_(A)) containing fluorocarbon radicals R_(F) are well knownand extensively described in the technical literature, for example inU.S. Pat. Nos. 3849521, 4742140, 5057577 and 5344903 and in EP-A 0198252and 0294648. Polycondensates (F_(B)) containing fluorocarbon radicalsR_(F) are likewise well known and described in the technical literature,for example in U.S. Pat. Nos. 3362782 and 3510455 and in EP-A 0073364.

It is preferred to use fluorocarbon polymers of the type (F_(A)) for theprocess of the invention. They are chiefly copolymers offluorocarbon-radicals-containing monomers (M1) of the formulae

 R_(F)—CH₂—CH₂—O—CH₂—CH₂—O—CH═CH₂  (V)

or

where

R₄ is C₁₋₁₂-alkyl,

R₅ is hydrogen or methyl,

R₆ is hydrogen or acetyl,

X is —CO — or —SO₂—,

Y is C₂₋₃-alkylene,

Z is C₁₋₁₂-alkylene,

x is zero or 1,

y is zero or 1 and

z is zero or 1,

and further ethylenically unsaturated non-ionogenic monomers, especially

(M2) ethylenically unsaturated non-ionogenic monomers which containlipophilic hydrocarbon radicals, for example (C₉₋₂₄-alkyl)(meth)acrylates, preferably (C₁₂₋₂₀-alkyl) (meth)acrylates,

and optionally

(M3) further non-ionogenic, ethylenically unsaturated monomers which arepreferably lower in molecular weight than the first two, for example(C₁₋₈-alkyl) (meth)acrylates (wherein alkyl radicals having 6 to 8carbon atoms may also by cyclic), vinyl chloride, vinylidene chloride,styrene, ethylene or propylene.

If desired, (F_(A)) may also contain minor proportions of

(M4) ethylenically unsaturated non-ionogenic comonomers which contain areactive moiety, chiefly a reactive hydrogen attached via a heteroatom(e.g. nitrogen, sulfur or oxygen) or an epoxy group,

as polymerized units. These reactive moieties are especially moietieswhich, after the copolymerization of the respective monomer, are capableof crosslinking with other parts of the polymer and/or with thesubstrate and are, for example, hydroxyl, thiol or epoxy groups, eachattached via a hydrocarbon radical, and/or a secondary amide group.

Suitable comonomers (M4) are chiefly comonomers (M4 a) of the formula

CH₂═CR₅—CO—O—R₇  (VII),

where

R₇ is hydroxy-C₂₋₄-alkyl, —(CH₂—CH₂—O)_(t)—H, dihydroxy-C₃₋₅-alkyl,3-chloro-2-hydroxypropyl or glycidyl and

t is from 1 to 20

or (M4b) comonomers of the formula

 CH₂═CH—CO—NH—CHR₈—OH  (VIII),

where R₈ is hydrogen, C₁₋₃-alkyl or ω-acetyloxy-C₂₋₄-alkyl, and theiralkyl ethers, for example (C₂₋₈-alkyl) ethers.

Preferred radicals R₇ are e.g. 2-hydroxyethyl, 2-hydroxypropyl,2,3-dihydroxypropyl, glycidyl, 3-chloro-2-hydroxypropyl and radicals ofthe formula —(CH₂—CH₂—O)₁—H, wherein t is from 1 to 10, preferably 1 to5.

R₈ is preferably hydrogen or 3-acetyloxy-2,2-dimethyl-1-hydroxy-propyl-1.

(M1) can be a single compound or also a mixture, for example a technicalgrade or random mixture, for example as described in U.S. Pat. Nos.3,849,521, 4,742,140 or 5,344,903.

Unlike the comonomers (M4), which contain a reactive moiety which, afterthe free-radical polymerization and after the application of the polymerto the substrate, is capable of crosslinking, the comonomers (M2) and(M3) do not contain such reactive moieties.

As (M2) can be employed one or also more compounds, for example thosedescribed in U.S. Pat. No. 5,344,903. Particular preference is given tolauryl (meth)acrylate and stearyl (meth)acrylate.

As (M3) can likewise be employed one or also more compounds, for examplethose described in U.S. Pat. Nos. 3,849,521 and 5,344,903 or in EP-A0,294,648, among which C₂₋₈-alkyl (meth)acrylates [particularly ethyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate], vinylchloride and vinylidene chloride are particularly preferred.

As (M4) can also be employed one or more comonomers, for example thosedescribed in U.S. Pat. Nos. 3,849,521 and 5,344,903 or in EP-A0,294,648, preferably at least one comonomer (M4a) and at least onecomonomer (M4b).

The weight ratio of the monomers is advantageously chosen so that theresulting copolymer has the desired water- and oil-repellent effect.Based on the total quantity of the comonomers [i.e. in particular (M1)and (M2) and, if present, (M3) and/or (M4)], the comonomers (M1) areused in an amount which is advantageously within the range from 25 to90% by weight, preferably within the range from 40 to 90% by weight,particularly preferably within the range from 40 to 75% by weight. Thecomonomers (M2) are used in an amount which is advantageously within therange from 5 to 50% by weight, preferably within the range from 15 to35% by weight, based on total comonomers. The comonomers (M3) are usedin an amount which is advantageously within the range from 5 to 50% byweight, preferably within the range from 5 to 25% by weight, based ontotal comonomers. A preferred embodiment also utilizes comonomers (M4)in minor proportions, advantageously up to 20% by weight based on totalcomonomers. The amount of (M4) employed is preferably 0.1 to 20% byweight, particularly preferably 2 to 15% by weight, for example 0.2 to5% by weight of (M4a) and 1.5 to 12% by weight of (M4b). Thecopolymerization can take place in a manner conventional per se,advantageously in aqueous emulsion in the presence of suitableemulsifiers and optionally solubilizers. Any suitable emulsifiers can beused, especially non-ionogenic and/or cationic emulsifiers. Examples ofsuitable non-ionogenic emulsifiers are addition products of ethyleneoxide with higher fatty alcohols (e.g. with 9 to 24 carbon atoms in thefatty radical) or with fatty acid partial esters of oligoalkanols suchas glycerol, sorbitol or sorbitan wherein the fatty acid radicalsadvantageously contain 12 to 24 carbon atoms. The HLB value of thenon-ionogenic surfactants is advantageously ≧10, preferably within therange from 12 to 18. Examples of cationic surfactants are simple fattyamines having, for examples, 12 to 24 carbon atoms in the fatty radical,or protonation or quaternization products thereof. Small amounts of theemulsifiers are sufficient for the polymerization in aqueous emulsion,for example 1 to 20% by weight, preferably 2 to 15% by weight, based onthe total monomers or respectively on (F).

When solubilizers are used, their concentrations are advantageouslywithin the range from 5 to 50% by weight based on total monomers or on(F). Examples of suitable solubilizers are customary compounds asmentioned above as (L), for example mono- or oligoalkylene glycols andtheir lower alkyl ethers. If desired or required, other customaryadditives are used for the polymerization, for example polymerizationregulators and/or catalysts.

The polymerization advantageously takes place at elevated temperature,for example within the temperature range from 40 to 90° C.,advantageously under an inert atmosphere, for example under nitrogen.The amount of water for the emulsion polymerization is advantageouslychosen so that an (F)-dispersion of the desired concentration isproduced, for example of a concentration within the range from 5 to 50%by weight, advantageously 10 to 40% by weight, preferably 15 to 30% byweight. The desired emulsion form can expediently also be obtained bysuitable stirring.

The mixtures (G) of the invention serve as additives for improving theoil- and water-repellent effect of (F)-finishes and their fastnesses,especially fastnesses to cleaning. Suitable substrates for the finish ofthe invention include any materials known to be given an oil- andwater-repellent finish with fluoro-carbon polymers, for example fibrousmaterials composed of natural, semisynthetic or fully syntheticmaterials, especially optionally modified cellulose (e.g. cotton, hemp,jute, viscose rayon, cellulose acetates) and blends thereof withsynthetic fibres (especially cotton/polyester, cotton/polyamide,cotton/polyurethane, cotton/viscose, cotton/polyester/polyurethane), andsynthetic fibres (e.g. polyamide, polyester, polyacrylonitrile). Thefibrous materials can be present in any desired suitable processing formused for finishing with fluorocarbon polymers, especially as wovens,knits, carpets, felts, webs and nonwovens, or else textiles coated witha polymeric film as are used for example for manufacturing weatherproofproducts (raincoats, anoraks, windcheaters, tents, tarpaulins, etc.), orproducts which are cleaned by shampooing (e.g. carpets, upholsterycovers). The finishing can be carried out before or also after themaking up.

The mixtures (G) of the invention are advantageously applied togetherwith (F) to the substrate to be finished; for this purpose, it ispossible to combine them, advantageously in the form of their aqueousdispersions (D), with (F) in a suitable treatment liquor, or (D) can forexample be formulated beforehand with (F) to form a stock liquor, or (D)can be formulated with a polymer (F) during or after the synthesis of(F) into an aqueous, concentrated composition. The polymers (F) areadvantageously employeded in the form of aqueous dispersions (which mayinclude conventional additives, such as emulsifiers or solubilizers)whose concentration of (F) is for example within the range from 5 to 50%by weight, preferably 10 to 40% by weight. The aqueous compositions (P)comprising (G) and (F), especially the concentrated compositions (P1),the prediluted compositions (P2) (especially stock liquors) and thediluted compositions (P3) (particularly treatment liquors), likewiseform part of the subject-matter of the present invention. Thesecompositions, especially (P1), advantageously comprise at least onecomponent (L) and/or (Z) which may each derive for example from theproduction of a corresponding (F)-dispersion and/or from the productionof (D), or may also be added separately.

The weight ratio of (G) to (F) is advantageously chosen so that a markedimprovement in the effect of (F) in the finish is brought about. Theweight ratio of (G)/(F) is advantageously within the range from 5/100 to120/100, preferably 10/100 to 90/100, particularly preferably 20/100 to70/100.

The concentration of [(G) +(F)] in the aqueous compositions (P) can varywithin wide limits, for example within the range from 0.1 to 70% byweight.

The concentration of [(G) +(F)] in the concentrated, aqueouscompositions (P1) comprising (G) and (F) is for example within the rangefrom 10 to 70% by weight, preferably from 15 to 50% by weight, based onthe total composition (P1). In the prediluted, aqueous compositions (P2)comprising (G) and (F), the concentration of [(G) +(F)] is for examplewithin the range from 0.3 to 30% by weight, preferably 1.5 to 15% byweight, based on the total composition (P2). In the aqueous treatmentliquors comprising (G) and (F), i.e. in the compositions (P3), theconcentration of [(G) +(F)] is for example from 0.1 to 10% by weight,preferably 0.2 to 5% by weight, based on the total composition (P3).

If desired, the finish may be combined with another customary syntheticresin finish, for example a synthetic resin finish based on optionallycyclic methylolureas or methylolmelamines or also precondensatesthereof, for example as described above as precursors for the productionof (F_(B)). If the finishing is carried out in the presence of syntheticresin, the corresponding synthetic resin precursor and any catalystwhich may be required may also be present in (P3).

The pH of the treatment liquor can vary within wide limits, for examplewithin the range from 2.5 to 8, preferably 4 to 7.5, in which thecorresponding suitable or optimal pH can be chosen according to theselected finish combination.

The finishing can be effected in a manner conventional per se, chieflyby means of impregnation processes, for example by padding, by dipping,by spraying, by knife-coating or by curtain coating, and similarcontinuous or discontinuous processes. The presence of the additive (G)or respectively (D) according to the invention makes it possible toreduce the amount of polymer (F) required, especially the requisiteminimum or optimum amount to obtain effective results, to a substantialextent. The concentration of (F) based on the dry substrate is forexample within the range from 0.1 to 5%, preferably 0.2 to 3%, byweight. The application of the treatment liquor to the substrate can befollowed by a suitable thermofixation as required for the respectivepolymers (F) and optionally synthetic resin, for example within thetemperature range from 110 to 220° C., preferably 120 to 200° C., forexample for 10 seconds to 2 minutes, an optimal fixation temperature andtime being choosable as a function of the type and consistency of thesubstrate, the presence or absence of synthetic resin, and thecomposition and concentration of the liquor. The thermofixation isadvantageously preceded by predrying, for example within the temperaturerange from 100 to 140° C., for example for 30 seconds to 5 minutes.

The presence of the additive (G) or respectively (D) of the inventionmakes it possible to enhance the effect of the (F) finish and improveits fastnesses, or respectively to substantially reduce the amount ofpolymer (F) required for achieving a certain effect level. This meansthat (G), preferably in the form of (D), can be used as an effectiveextender or blending agent for (F), so that a minimal amount offluorocarbon polymer (F) can be used to obtain optimal oil- andwater-repellent finishes which, moreover, have noteworthy fastnesses,especially fastnesses to cleaning (chiefly fastnesses to shampooing andwashing), while the specific properties are practically unimpaired ormay even be improved. Owing to the particularly good fastnesses tocleaning, it is additionally also possible for the finished materials tobe for example washed in a domestic washing machine (e.g. windcheatersor raincoats and the like) and air dried or also tumble dried, or to beshampooed (e.g. carpets, upholstery covers and the like) and air dried,without a subsequent heat treatment, for example ironing, beingabsolutely necessary.

In the Examples hereinbelow, parts and percentages are by weight and thetemperatures are reported in degrees Celsius.

EXAMPLES Examples 1 to 5 Production of Mixtures (G) and Dispersions (D)Example 1

222.1 parts of a hexamethylene diisocyanate/biuret prepolymer (having aviscosity of 10,000 mPas at 23° C., a functionality of 3.7 and anisocyanate-based equivalent weight of 192) are reacted at 70° C. undernitrogen with 40.5 parts of polyethylene glycol monomethyl ether(hydroxyl number=75) until an equivalent weight (based on -NCO) of 267is present. The product is then cooled down to 40-50° C., and 97.4 partsof 3,5-dimethylpyrazole are added. After 3 hours at 50° C. there are nofurther free titratable isocyanate groups. 830 parts of water are thenadded to obtain about 1190 parts of a fine, milky dispersion.

Example 2

47.45 parts of a methylenephenyl isocyanate prepolymer (having aviscosity of 600 mPas at 25° C., a functionality of 2.9 and anisocyanate-based equivalent weight of 138) are reacted at 80° C. undernitrogen with 12.55 parts of polyethylene glycol monomethyl ether(hydroxyl number=75) until an equivalent weight of 193 (based on NCOgroups) is obtained. Concurrently, 203.88 parts of hexamethylenediisocyanate polyisocyanurate (trimer having a viscosity of 3000 mPa at23° C., a functionality of 3.7 and an equivalent weight of 197.5) arereacted at 80° C. under nitrogen with 36.12 parts of polyethylene glycolmonomethyl ether (hydroxyl number=75) until an equivalent weight (basedon NCO groups) of 252 is present. The two reaction products are thenmixed together and admixed at 40 to 50° C. with 125 parts of3,5-dimethylpyrazole. After 3 hours there are no titratable isocyanategroups left, and 21 parts of an ethylene oxide/propylene oxide blockcopolymer having a hydroxyl number of 25.5, a molecular weight of 4400and a polyethylene glycol weight fraction of about 10% are added. Thisis followed by the addition of 957 parts of water at 50° C., and thebatch is allowed to cool. 1403 parts of a fine milky dispersion areobtained.

Example 3

237 parts of a hexamethylene diisocyanate polyisocyanurate (trimerhaving a viscosity of 3000 mPas at 23° C., a functionality of 3.7 and anequivalent weight based on NCO groups of 197.5) are reacted at 70° C.under nitrogen with 42 parts of polyethylene glycol monoethyl ether(hydroxyl number=75) until an equivalent weight (based on NCO groups) of268 is present. The batch is then cooled down to 40-50° C., 103 parts of3,5-dimethylpyrazole are added, and the reaction is left to proceed tocompletion over 3 hours. Then 19 parts of isooctylphenolpoly-10-ethylene glycol ether are added, followed by 545.5 parts ofwater at 50° C., and the batch is allowed to cool down to roomtemperature. 947.5 parts of a very fine dispersion are obtained which isstable in storage.

Example 4

512.2 parts of hexamethylene diisocyanate polyisocyanurate (trimeralongside penta- and heptamer) (having a viscosity of 3650 mPas at 23°C. and an equivalent weight based on NCO groups of 195.3) are mixed at50° C. with 90 parts of polyethylene glycol monomethyl ether (hydroxylnumber=73) and then admixed with 144 parts of acetone. A clear solutionis obtained which has a temperature of 31° C. Then 0.59 part ofdibutyltin diacetate is added, and the temperature rises to 37° C. inthe course of a few minutes. Then 3.2 parts of water are added, and thetemperature rises to 36° C. It is then raised to 41-43° C., and CO₂ isfound to evolve. As soon as the evolution of gas ceases, which is thecase about 60 minutes after the addition of the water, a start is madeon the addition of 206.1 parts of 3,5-dimethyl-pyrazole. The additiontakes 1 hour during which the temperature is maintained below 53° C. Thebatch is then heated to 60° C., and the acetone is distilled off at thattemperature. A clear, viscous mass is obtained which is admixed with40.3 parts of tridecanol poly-6.5-ethylene glycol ether and cooled to45° C. Then 1168 parts of water at 45° C. are added over 60 minutes withvigorous stirring. A fine, milky dispersion is obtained which is allowedto cool down to room temperature.

Example 5

512.2 parts of hexamethylene diisocyanate polyisocyanurate (trimeralongside penta- and heptamer) (having a viscosity of 3650 mPas at 23°C. and an equivalent weight based on NCO groups of 195.3) are mixed at50° C. with 90 parts of polyethylene glycol monomethyl ether (hydroxylnumber=73) and then admixed with 144 parts of acetone. A clear solutionis obtained which has a temperature of 31° C. Then 0.59 part ofdibutyltin diacetate is added, and the temperature rises to 37° C. inthe course of a few minutes. Then 11.02 parts of anhydrous ethyleneglycol, dissolved in 66 parts of acetone, are added, and the temperatureis raised to 50° C. The batch is then left to react at 50° C. until theethylene glycol has completely reacted with the polyisocyanate, whichrequires about 60 minutes. Then 206.1 parts of 3,5-dimethylpyrazole areadded over 1 hour at 45 to 50° C. so that the temperature stays below53° C. The batch is then heated to 60° C., and the acetone is distilledoff at that temperature. A clear, viscous mass is obtained which isadmixed with 40.3 parts of tridecanol poly-6.5-ethylene glycol ether andcooled to 45° C. Then 1168 parts of water at 45° C. are added over 60minutes with vigorous stirring. A fine, runny, milky dispersion isobtained which is cooled down to room temperature.

Examples 6 to 10 Production of Products (F) and their DispersionsExample 6

A flask is charged with a mixture of the following compounds:

125 g of monomer of the formula CF₃—(CF₂)_(q)—(CH₂)₂—O—CO—C(CH₃)═CH₂(mixture of compounds where q=7, 9 and 11 ina weight ratio of 5:3:1),

100 g of CH₂═CH—CO—O—C₁₈H₃₇,

1 g of CH₂═CH—CO—O—C₁₂H₂₅,

17 g of N-methylolmethacrylamide,

6 g of glycidyl methacrylate,

10 g of N-butoxymethylmethacrylamide,

586 g of deionized water,

120 g of dipropylene glycol methyl ether,

1 g of n-dodecyl mercaptan,

15 g of stearylamine acetate and

5 g of poly-(20)-oxyethylene sorbitan monooleate,

and the mixture is initially stirred for 1 hour at 60° C. under a streamof nitrogen to form a fine emulsion. After addition of 9 g ofazobisisobutylamidine hydrochloride in 25 g of water the batch isstirred for 4 hours at 55° C. in a stream of nitrogen while thepolymerization proceeds. Gas chromatography confirms that the conversionis more than 99%. The dispersion obtained contains the fluorocarboncopolymer in a concentration of 25.8% by weight.

Example 7

Example 6 is repeated with the difference that a mixture of thefollowing compounds is employed:

43.5 g of monomer of the formula CF₃—(CF₂)_(q)—(CH₂)₂—O—CO—C(CH₃)═CH₂(mixture of compounds where q=7, 9 and 11 in a weight ratio of 5:3:1),

8 g of CH₂═CH—CO—O—C₁₈H₃₇,

8 g of CH₂═CH—CO—O—C₁₂H₂₅,

5.28 g of N-methylolmethacrylamide,

1.76 g of glycidyl methacrylate,

0.88 g of N-butoxymethylmethacrylamide,

262.8 g of deionized water,

32 g of dipropylene glycol,

0.2 g of n-dodecylmercaptan,

3.2 g of stearylamine acetate and

1.6 g of poly-(20)-oxyethylene sorbitan monooleate.

The dispersion obtained contains the fluorocarbon copolymer in aconcentration of 17.8% by weight.

Example 8

A flask is charged with a mixture of the following compounds:

125 g of monomer of the formula CF₃—(CF₂)_(q)—(CH₂)₂—O—CO—C(CH₃)═CH₂(mixture of compounds where q=7, 9 and 11 in a weight ratio of 5:3:1),

35 g of CH₂═CH—CO—O—C₁₈H₃₇

17 g of N-methylolmethacrylamide,

5 g of glycidyl methacrylate,

11 g of N-butoxymethylmethacrylamide

580 g of deionized water

120 g of dipropylene glycol methyl ether

0.8 g of n-dodecyl mercaptan

10 g of stearylamine acetate and

15 g of poly(-20)-oxyethylene sorbitan monooleate,

and the mixture is initially stirred for 1 hour at 60° C. under a streamof nitrogen to form a fine emulsion. Then, 50 g of vinylidene chlorideare added and, after addition of 9 g of azobisisobutylamidinehydrochloride in 25 g of water, the batch is stirred for 4 hours at 55°C. in a stream of nitrogen while the polymerization proceeds. Gaschromatography confirms that the conversion is more than 99%. Thedispersion obtained contains the fluorocarbon copolymer in aconcentration of 25.8% by weight.

Example 9

Aqueous 21% dispersion of the copolymer of 14% of perfluoroacrylate asin Example 6, 5% of vinyl chloride and 2% of 2-ethylhexyl acrylate,additionally containing 1% of emulsifiers.

Example 10

Aqueous dispersion containing 30% of the copolymer of 21% ofperfluoroacrylate as in Example 6, 6% of vinyl chloride and 3% offurther components (emulsifiers and crosslinking monomers) and 15% ofdipropylene glycol.

Examples 11 to 25 Production of Compositions (P) Example 11

200 parts of the fluorocarbon polymer dispersion obtained according toExample 6 are mixed with 40 parts of the dispersion obtained accordingto Example 1. The formulation obtained is stable in storage.

Examples 12 to 15

200 parts of the fluorocarbon polymer dispersion obtained according toExample 6 are mixed with 40 parts of the dispersion obtained accordingto Example 2, 3, 4 or 5. The formulations obtained are stable instorage.

Examples 16 to 25

Analogously as in Examples 11 to 15, the fluorocarbon copolymerdispersions according to Examples 7 to 10 are employed in place of thefluorocarbon polymer dispersion obtained according to Example 6. Theformulations obtained are also stable in storage.

Application Example A

A 122 g/m² cotton cretonne fabric (bleached) is padded on a Mathis HVF41496 laboratory pad-mangle with an aqueous liquor of the followingcomposition:

5 g/l of product according to Example 1, 2, 3, 4 or 5

20 g/l of fluorocarbon copolymer dispersion prepared according toExample 6

2 ml/l of 60% acetic acid

to a pick-up of 80% and then dried and flash cured (180° C./30 secondseffective time) on a Mathis LTE 21496 Lab dryer. The samples are thenconditioned (24 hours, 65% relative humidity, 20° C.). Half are thenwashed five times (40° C., ISO standard 6330) and then dried (1 minute,140° C., Mathis LTE 24196 Lab dryer) and pressed at 160° C. for 20seconds (Schröter Press).

The oil test and spray test ratings of the washed samples determinedaccording to the standard test methods AATCC 22 and AATCC 118 aresignificantly higher than those of the respective blanks (i.e. withoutthe product of Example 1, 2, 3, 4 or 5).

Application Example B

A 122 g/m² cotton cretonne fabric (bleached) is padded and treated inthe same way as described in Application Example A with an aqueousliquor of the following composition:

10 g/l of product according to Example 1, 2, 3, 4 or 5

30 g/l of fluorocarbon copolymer dispersion prepared according toExample 6

20 g/l of dihydroxyethylene-N,N′-dimethylolurea

5 g/l of magnesium chloride hexahydrate

2 ml/l of 60% acetic acid.

The oil test and spray test ratings of the washed samples determinedaccording to the standard test methods AATCC 22 and AATCC 118 aresignificantly higher than those of the respective blanks (i.e. withoutthe product of Example 1, 2, 3, 4 or 5).

Application Example C

Polyester/cotton gabardine (67/33) is padded in the same way as inApplication Example A with an aqueous liquor of the followingcomposition:

20 g/l of fluorocarbon copolymer dispersion prepared according toExample 6

10 g/l of product according to Example 1, 2, 3, 4 or 5

2 ml/l of 60% acetic acid

to a pick-up of 80% and then dried and flash cured (180° C./30 secondseffective time) on a Mathis LTE 21496 Lab dryer. The samples are thenconditioned (24 hours, 65% relative humidity, 20° C.). Half are thenwashed five times (40° C., ISO standard 6330) and then dried (1 minute,140° C., Mathis LTE 24196 Lab dryer) and pressed at 160° C. for 20seconds (Schröter Press).

The fastness ratings of the washed samples, determined according to theDIN 5388 standard method (Bundesmann short shower test—bead-off effectafter 1 minute and after 10 minutes), are significantly higher thanthose of the respective blanks (i.e. without the product of Example 1,2, 3, 4 or 5).

Application Example D

Polyamide taffeta is padded and treated in the same way as described inApplication Example A with an aqueous liquor of the followingcomposition:

30 g/l of the mixture prepared according to Example 11

2 ml/l of 60% acetic acid.

The oil test and spray test ratings of the washed samples determinedaccording to the standard test methods AATCC 22 and AATCC 118 aresignificantly higher than those of the respective blanks (i.e. withoutthe product of Example 11).

Instead of the fluorocarbon copolymer dispersion of Example 6, thecorresponding amounts of fluorocarbon copolymer dispersion according toExample 7, 8, 9 or 10 or also commercially available fluorocarboncopolymer dispersions such as: Oleophobol S (Pfersee Chemie, Germany),Zepel 8070 (DuPont, USA), Asahi Guard AG 310, 915 or 923 (Asahi Glass,Japan) or Rucogard AFS or AFC (Rudolf Chemie, Germany) may be employedin Application Examples A, B and C.

Oil test and spray test ratings are obtained on the washed samples whichare also significantly higher than those of the respective blanks (i.e.without the product of Example 1, 2, 3, 4 or 5).

In Application Example D, instead of the mixture of Example 11,corresponding amounts of the mixtures according to Examples 12-25 may beemployed.

What is claimed is:
 1. A mixture (G), self-dispersible in water, ofoligomeric isocyanates (C) reacted in part with polyethylene glycolmonoalkyl ether (A), which optionally contains propyleneoxy units, andoptionally with a chain extender (K) and exhaustively blocked with anisocyanate-blocking pyrazole (I).
 2. A mixture (G) according to claim 1,wherein the polyethylene glycol monoalkyl ethers (A), which optionallycontain propyleneoxy units, conform to the average formula R—(O—CH₂—CH₂)_(n)—OH  (I) where R is C₁₋₄-alkyl-(O-propylene)_(m)—, nis from 5 to 30 and m is from 0 to 10, with the proviso that m is ≦⅓ ofn.
 3. A mixture (G) according to claim 1, characterized in that (K) iswater.
 4. A process for the production of mixtures (G) according toclaim 1, characterized in that in a first process step (a) a minorproportion of the isocyanate groups in the oligomeric isocyanate (C) arereacted in the absence of protogenic solvents with polyethylene glycolmonoalkyl ether (A), which optionally contains propyleneoxy units, toform a product (U1) and this product (U1) is then optionally convertedinto a product (U2) which has a higher NCO-based equivalent weight andwhich still contains reactive NCO groups, and in a second process step(b) the remaining isocyanate groups are exhaustively blocked withisocyanate-blocking pyrazole (B).
 5. A process according to claim 4,characterized in that the equivalents ratio of (A)/(C) is within therange from 1:2 to 1:50.
 6. A process according to claim 4, characterizedin that in process step (a) the treatment of (U1) is carried on at60-95° C. until the isocyanate-based equivalent weight of product (U2)has risen beyond that corresponding stoichiometrically to urethaneformation in (U1).
 7. A process according to claim 6, characterized inthat in process step (a) the treatment of (U1) is carried on at 60-95°C. until the isocyanate-based equivalent weight of product (U2) hasrisen by 1 to 20% beyond that corresponding stoichiometrically tourethane formation in (U1).
 8. A process according to claim 4,characterized in that in process step (a) (U1) is reacted with a chainextender (K) in such a way that the isocyanate-based equivalent weightof product (U2) is 1 to 20% higher than that correspondingstoichiometrically to urethane formation in (U1).
 9. The mixtures (G)obtainable by the process of claim
 4. 10. An aqueous dispersion (D) of amixture (G) according to claim
 1. 11. An aqueous dispersion (D)according to claim 10, further comprising a non-ionogenic,surface-active stabilizer (E) and/or a solubilizer (L) and/or anadditive (Z) to control microbial damage.
 12. A process for theproduction of aqueous dispersions (D) according to claim 10,characterized in that a mixture (G) of oligomeric isocyanates (C)reacted in part with polyethylene, glycol monoalkyl ether (A), whichoptionally contains propyleneoxy units, and optionally with a chainextender (K) and exhaustively blocked with an isocyanate-blockingpyrazole (B), is mixed with water and optionally admixed with at leastone further additive.
 13. A method for the application of a mixture (G),self-dispersible in water, of oligomeric isocyanates (C) reacted in partwith polyethylene, glycol monoalkyl ether (A), which optionally containspropyleneoxy units, and optionally with a chain extender (K) andexhaustively blocked with an isocyanate-blocking pyrazole (B),comprising providing (G) as an auxiliary in the finishing of fibrousmaterial with oleophobicizing and/or hydrophobicizing finishing agents(F) which are fluorocarbon-radicals-containing polymers.
 14. The methodaccording to claim 13, characterized in that (G) and (F) are provided inthe form of an aqueous composition (P) containing (G) and (F).
 15. Anaqueous composition (P) comprising (G) and (F), wherein (G) is amixture, self-dispersible in waters of oligomeric isocyanates (C)reacted in part with polyethylene, glycol monoalkyl ether (A), whichoptionally contains propyleneoxy units, and optionally with a chainextender (K) and exhaustively blocked with an isocyanate-blockingpyrazole (B), and (F) is an oleophobicizing and/or hydrophobicizingfinishing agent which is a fluorocarbon-radicals-containing polymer. 16.A process for the finishing of textile material by impregnation methodsfrom an aqueous liquor, optionally together with a synthetic resinfinish, with thermofixation, comprising contacting the textile materialwith the mixture (G) of claim
 1. 17. A method for the application of anaqueous dispersion (D) of a mixture (G), self-dispersible in water, ofoligomeric isocyanates (C) reacted in part with polyethylene, glycolmonoalkyl ether (A), which optionally contains propyleneoxy units, andoptionally with a chain extender (K) and exhaustively blocked with anisocyanate-blocking pyrazole (B), comprising providing the mixture (G)in said aqueous dispersion (D) as an auxiliary in the finishing offibrous material with oleophobicizing and/or hydrophobicizing finishingagents (F) which are fluorocarbon-radicals-containing polymers.